DE3431926A1 - AMIDINOAZOLE - Google Patents

Description

BAYER AKTIENGESELLSCHAFT · if. 5090 Leverkusen, Bayeru / Erk

Corporate administration RP Bi / mm

Patent Department IUb

3 υ

.AUG. 198V

Amidinoazoles

The invention relates to new amidinoazoles, an inventive one l / learn about their production and their use as herbicides.

Various amidinoazole derivatives are as potential Herbicides have become known, however, have hitherto been used as a means of controlling weeds and / or regulating plant growth no greater importance achieved (cf. DE-PS 2 321 330).

There were now new amidinoazoles of the general formula (I)

R ^ SO ₂ -N ^ ^H -; NR ² _(I)

Az

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in vi / elcher

R is an optionally substituted radical from Series alkyl, aralkyl, aryl and heteroaryl,

R represents an optionally substituted and / or optionally fused six-membered aromatic heterocycle containing at least one nitrogen atom contains, stands and

Az is an optionally substituted azole radical, d. H. a five-membered aromatic heterocycle, which contains at least one nitrogen atom,

as well as adducts of compounds of the formula (I) with strong acids found.

The general formula (I) stands for the individual tautomers of formulas (IA) and (IB)

R ¹ -SO ₂ -N _V / NH-R ²

^ CT (IA)

Az

R ¹ -SO ₂ -NH

Az

in which

1 2

R, R and Az have the meanings given above ^ and for mixtures of the tautomers (IA) and (IB).

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The mixing ratio (IA) / (IB) depends on the aggregation-determining factors Factors u / ie z. B. temperature, solvent and focus.

The new amidinoazoles of the formula (I) are obtained according to an inventive method when using sulfonylguanidine derivatives of formula (II)

R ¹ -S0 ₂ -N ^ 'NR ² C

R ¹ -S0 ₂ ^{/ N} 0-R ³

in which

1 2 R and R have the meanings given above and

R stands for an optionally substituted hydrocarbon radical stands,

with compounds of the formula (III)

M-Az (III)

in which Az has the meaning given above and M stands for hydrogen or a metal equivalent,

optionally in the presence of bases and in the presence of diluents at temperatures between 0 ⁰ C and 100 ⁰ C and optionally the resulting

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Products of formula (I) treated with acids.

The new amidinoazoles of the formula (I) and their adducts with strong acids are characterized by strong herbicidal effectiveness.

Surprisingly, the new connections of the Formula (I) considerably better herbicidal action than previously known amidinoazole derivatives with the same direction of action.

It is also to be regarded as surprising that the invention Compounds of the formula (I) by selective cleavage of sulfonylguanidine derivatives of the formula (II) can be produced, as in addition to this novel reaction also other cleavage reactions, for example by attack on the sulfonyl groups was.

The invention preferably relates to compounds of formula (I) in which

R stands for the remainder Π \\ -, in which

R and R are identical or different and represent hydrogen, halogen [such as in particular fluorine, Chlorine and / or bromine], cyano, nitro, C-i-Cß-

Alkyl [which may be replaced by fluorine, Chlorine, bromine, cyano, carboxy, C-i-C ^ -alkoxycarbonyl, C-i-C ^ -alkylamino-carbonyl, di- (Ci-Ci, .- alkyl ) -amino-carbonyl, hydroxy, C-1-C ^ -alkoxy, formyloxy, Ci-C ^ -alkyl-car-

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- γ-

- r

bonyloxy, Ci-C ^ -alkoxy-carbonyloxy, Ci-C ^ - Alkylamino-carbonyloxy, C-i-C ^ -alkylthio, C-i-C ^ -Alkylsulfinyl, Ci-C ^ -Al kylsul f onyl, Di- (Ci-C ^ -alkyl) -aminosulfonyl, C3-C6-cycloalkyl or phenyl is substituted],

for C2-Cg-alkenyl [which is optionally _{substituted by fluorine, chlorine, bromine, cyano, C 1} -C * ,, - alkoxycarbonyl, carboxy or phenyl], for Ci-Cif-alkoxy [which is optionally substituted by fluorine, chlorine , Bromine,

Cyano, carboxy, CjC ^ -alkoxycarbonyl, Ci-Cz ₊ -Alkylthio, Ci-C ^ -Alkylsulfinyl or Ci-Cit-Alkylsul f onyl is substituted], for C3-Cß-alkenoxy [which optionally by fluorine, chlorine, Bromine, cyano or

C1-Ci ^ -alkoxy-carbonyl is substituted], Cs-Cß-alkynoxy, for the radical -S (0) _p -R ⁶ , where

ρ stands for the numbers zero, 1 or 2 and

R for Ci-C ^ -alkyl [which is optionally substituted by fluorine, chlorine, bromine, cyano or Ci-C ^ -alkoxycarbonyl], C ₃ -C6-alkenyl, C3-C ₆ -alkynyl, Ct -Ctf. -Alkoxy, CiC / f-alkoxyamino,

C ₁ -C ^ -AIkOXy-C ₁ -C ^ -alkyl-amino, CiC ^ -alkylamino or di- (CjC ^ -alkyl) -amino,

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for phenyl or phenoxy, for CjC ^ -alkylcarbonylamino, CjC ^ -alkoxy-carbonylamino, Ci-C ^ -alkylamino-carbonyl-amino, di- (C ₁ -C ^ - alkyl) -amino-carbonylamino, for the remainder -CO -R ⁷ , where

R ⁷ for Ci-C ₆ -alkyl, C ₁ -C ₆ -AIkOXy, C ₃ -C ₆ -alkenoxy, CiC ^ -alkyl thio, C ^ -Ct ₊ - Alkyl.amino, CiC ^ -alkoxyamino, Ct-Cz ^ -AIkOXy-C ₁ -C ^ -alkyl-amino or di-CCi-C ^ -alkyl) -amino [which

are optionally substituted by fluorine and / or chlorine],

for Ci-C ^ -Alkylsulfonyloxy, di- (C ₁ -C ^ aI-kyl) -aminosulfonylamino or for the remainder -P = NR ⁸ , where

R ⁹

R for optionally substituted by fluorine, chlorine, cyano, carboxy, CjC ^ -alkoxy, carbonyl, C ₁ - Ci, -Alkyl thio, Ci-Cit-Alkylsulfinyl or CjC ^ -Alkylsul fonyl, for optionally

benzyl substituted by fluorine or chlorine, for C ₃ -C ₆ alkenyl or C ₃ -C ₆ alkynyl which is optionally substituted by fluorine or chlorine, for optionally by fluorine, chlorine, bromine,

CiC ^ alkyl, CiC ^ alkoxy, trifluoromethyl, trifluoromethoxy or trifluoromethylthio substituted phenyl, for optionally substituted by fluorine and / or chlorine C ₁ -C ₆ alkoxy,

Cs-Ce-alkenoxy, C ₃ -C ₆ -AlkInOXy or

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Benzyloxy, for amino, C-i-C ^ -alkylamino, Di-CC-i-C ^ -alkylJ-amino, phenyl amino, Ci-C ^ -alkyl-carbonyl-amino, C-j-Ci, .- alkoxy-carbonylamino, Ci-C ^ alkylsulfonylamino or for if applicable

phenylsulfonylamino substituted by fluorine, chlorine, bromine or methyl stands and

R 'stands for hydrogen or C ₁ -C ^ -alkyl? in what further

R represents the radical -CH ( ^{7 5} O, in which

R represents hydrogen or C- | -C ₃ -alkyl,

12th

R and R are identical or different and represent hydrogen, fluorine, chlorine, bromine, nitro, cyano, C ι-Cz ₊ -Al ky 1 [which optionally

is substituted by fluorine and / or chlorine], Ci-Cv-alkoxy [which optionally is substituted by fluorine and / or chlorine], carboxy, Ci-C ^ -alkoxy-carbonyl, Ci-C ^ -Alkylsulfonyl or Di- (C τ-C ^ -alky1) -

aminosulfonyl; in what further

R ^{1 stands} for the remainder —fy U jf] , in which

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-A

R and R are identical or different and represent hydrogen, Fluorine, chlorine, bromine, nitro, cyano, C-j-C 1-4 alkyl [which optionally is substituted by fluorine and / or chlorine] or C-i-C ^ -alkoxy [vi / elches optionally is substituted by fluorine and / or chlorine]; in what further

R stands for the remainder l ^^ J, in which

16

R and R are identical or different and represent hydrogen, Fluorine, chlorine, bromine, nitro,

Cyano, Ci-C ^ -alkyl [which optionally is substituted by fluorine and / or chlorine], Ci-Ci ^ -alkoxy [which optionally is substituted by fluorine and / or chlorine], for d-C ^ -alkylthio,

C-i-Ci ^ -alkylsulfinyl or C-i-C ^ -alkylsulfonyl [which are optionally substituted by fluorine and / or chlorine], as well as for di-CC-i-C ^ -alkyl) -aminosul fony 1 or Ci-Cif-alkoxy-carbonyl stand; wherein

Further

stands for the remainder - XC if "^ L, in which

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18th

R and R are identical or different and represent hydrogen, Fluorine, chlorine, bromine, C-j-C ^ -alkyl [which is optionally substituted by fluorine and / or bromine], C-j-C 1-4 alkoxy [which if necessary by fluorine and /

or chlorine is substituted], for Ci-C ^ - alkylthio, Ci-Ci _4. -Alkylsul f iny 1 or Ci-C ^ -Alkylsulfony1 [u / which are optionally substituted by fluorine and / or chlorine] or for di ( Ci-C ^ -alkyl) -aminosul-

fonyl stand; in what further

-R ^{1 9}
stands for the radical -L · -H ", in which

R and R are identical or different and represent hydrogen, Fluorine, chlorine, bromine, cyano, nitro, C1 -C4 alkyl [which optionally

substituted by fluorine and / or chlorine], Ci-Cif-alkoxy [which is optionally substituted by fluorine and / or chlorine], CiC ^ -Alkylthio, C ₁ -C ^ -Alky lsul finyl or Ci-C ^ -Alkylsulfonyl [ which

optionally by fluorine and / or chlorine is substituted], di- (Ci-C ^ -alky1) -aminosulfonyl or C-j-C ^ alkoxy-carbonyl stand, and

Z for oxygen, sulfur or the group

pation NZ ¹ , where

Z for hydrogen, Ci-C ^ -alkyl [which

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optionally substituted by fluorine, "chlorine, bromine or cyano], C ₃ -C ₆ -cycloalkyl, benzyl, phenyl [which is optionally substituted by fluorine, chlorine, bromine or nitro], C -C -alkyl-carbonyl, C ₁ -Ci ₊ - alkoxycarbonyl or di- (Ci-C ^ -alkyl) -aminocarbonyl stands;

in what further

_R 21
R stands for the radical -O MR ²² , in which

23

and R are the same or different and for what

hydrogen, fluorine, chlorine, bromine, CiC ^ -A [which is optionally substituted by fluorine and / or chlorine], or CI-Ci _4. -Alkoxy [which is optionally by

Fluorine and / or chlorine is substituted] with the proviso that at least one of the radicals R ²¹ and R ^{23 is} different from hydrogen, and

R ²² for hydrogen, fluorine, chlorine, bromine,

Cyano or C1 -C4 alkyl [which optionally is substituted by fluorine and / or chlorine]; in what further

stands for the remainder - ( ^{/ V} N, in which

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_η 24, _η 25 are identical or different and are what-R and R ^y

hydrogen, fluorine, chlorine, bromine, C ₁ -Ct, - Al kyl [which is optionally substituted by fluorine and / or chlorine], C ₁ -Ci ₊ -AIkOX [which is optionally substituted by fluorine and /

or chlorine is substituted], CjC ^ -alkylamino or di- (C ₁ -C ^ -alky1) -amino with the proviso that at least one of the radicals R and R ^{25 is} different from hydrogen; in what further

R ^{2 represents} the radical -If X) -R * ⁷ , in which

R for hydrogen, fluorine, chlorine, bromine,

Hydroxy, Ci-C ^ -alkyl [which optionally is substituted by fluorine and / or chlorine] or Ci-C ^ -Al koxy [which

optionally by fluorine and / or chlorine is substituted],

7th
R for hydrogen, fluorine, chlorine, bromine,

Ci-Ci ^ -Alky 1 [which if necessary by Fluorine and / or chlorine is substituted],

Cyano, formyl, Ci-C ^ -alkyl-carbony1 or C ₁ -C ^ -alkoxycarbonyl and

R for hydrogen, fluorine, chlorine, bromine, hydroxy,

[which is optionally substituted by fluorine and / or chlorine],

C ₁ -C ^ -AIkOXy [which is optionally substituted by fluorine and / or chlorine], amino, CjC ^ -alkyl-amino or di- (Cj-Cv-alkyl) -amino, or

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Ά

7 2 8

R and R together represent Cs-C ^ -alkanediyl;

in which further ~

_R 29

^N ;

R stands for the remainder - ('^ N, in which

^N R ³⁰

30th
R and R are identical or different and represent fluorine, chlorine, bromine, hydroxy, Ci-C ^ -

Alkyl [which optionally by Fluorine and / or chlorine is substituted], Cs-Cs-cycloalkyl, C-i-C ^ -alkoxy [which is optionally substituted by fluorine and / or chlorine], Cn-C ^ -alkylthio

or are Ct-C ^ -alkyl-amino or Qi- (C ₁ -C ^ -alky 1) -amino; in what further

Ν — Ν

R stands for the radical - / ^/ \) - R ³ⁿ , in which

NjzY

R ³²

32
R and R are identical or different and represent hydrogen, methyl or methoxy ;

in what further

Az stands for a radical from the series pyrazole, imidazole and triazole, u / elcher optionally by chlorine, bromine, iodine, nitro, C η-C ^ -alkyl [which is optionally substituted by fluorine and / or chlorine], Ct- Zi ₊ -Alkoxy [which is optionally substituted by fluorine and / or chlorine], Cη-C ^ -alkylthio [which is optionally

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is substituted by fluorine and / or chlorine] and / or phenyl [which is optionally substituted by fluorine, chlorine, bromine, iodine, CiC ^ -alkyl, tri fluoromethyl, C ₁ -Cz ₊ -AIkOXy, C1-C2-fluoroalkoxy, CjC ^ -Alkyl thio, trifluoromethylthio, cyano, nitro or CiC ^ -alkoxycarbonyl is substituted].

The invention furthermore preferably relates to adducts of compounds of formula (I) - as defined above - with hydrohalic acids, such as hydrogen fluoride, Hydrogen chloride, hydrogen bromide, hydrogen iodide, with Sulfuric acid, with optionally by fluorine and / or Chlorine substituted alkanesulfonic acids with 1 to 4 carbon atoms or also benzene or naphthalenesulfonic acids, which optionally by fluorine, chlorine, bromine or methyl are substituted.

The invention relates in particular to compounds of the formula (I) in which

(A) R stands for the radical ( ^{f X} V, in which

R for fluorine, chlorine, bromine, methyl, chloromethyl, trifluoromethyl, methoxy, difluoromethoxy, tri

fluoromethoxy, methylthio, methylsulfinyl, methyl sulphonyl, dimethylaminosulphonyl, phenyl or C-i-Cs-alkoxycarbonyl, and

R represents hydrogen; in what further

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R stands for the radical - / ^/ ^) - R ²⁷ , in which

R represents hydrogen, methyl, hydroxy, fluorine, chlorine, bromine or methoxy,

27
R stands for hydrogen, chlorine, bromine or methyl

stands and

R.
R for C ₁ -C ₃ alkYl, hydroxy, fluorine, chlorine, bromine

or C ₁ -C ₃ alkoxy; in what further

Az is an optionally substituted by methyl ated pyrazole or imidazole radical, or in which

(B) Az and R have the meanings given above under (A) and

R ²⁹
N ~ < ^R

R stands for the remainder - (/ ^ N, in which

29
R for fluorine, chlorine, bromine, hydroxy, methyl, cyclopropyl, methoxy, ethoxy, methylthio

or ethylthio and

R ^{30 represents} fluorine, chlorine, bromine, hydroxy, methyl, cyclopropyl, methoxy, ethoxy, methylamino, ethylamino, dimethylamino or diethylamino.

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If, for example, N '- (4,6-dimethyl-pyrimidin-2-yl) -N "-methoxy-N" -N ¹ "-bis-CZ-methoxycarbonyl-benzenesulfonyl) -guanidine and imidazole are used in the process according to the invention as starting materials, the course of the reaction can be sketched using the following equation:

COOCH ₃ CH

IN THE

r— \ N - / ^ VsO ₂ -NH-OCH ₃ ^ WX _OC " ₃ ^ COOCH ₃ ^ COOCH ₃

COOCH3 CH ₃

(/ VVSO ₂ -N v ^H -> N ^ / Λ

vzy ^ c ^x /

The starting materials used in the production process according to the invention The sulfonylguanidine derivatives to be used are generally defined by the formula (II). In this formula preferably have the residues

1 2
R and R have the same meanings as they are above in the frame

the definition of the corresponding radicals in the formula (I) are preferably mentioned and

R preferably represents C-i-C ^ -alkyl or benzyl.

Starting materials of the formula (II) are particularly preferred in which the remains

1 2
R and R have the same meanings as they are above in the frame

the definition of the corresponding radicals in formula (I) as are particularly preferred and

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R ^{3 represents} methyl.

Examples of the starting materials of the formula (II) are called:

N '- (4,6-Dimethyl-pyrimidin-2-yl) -N "-methoxy- -N ¹ ', N ¹ " -bis-U-chloro-benzenesulfonyl) -, -N ", N ¹ '' -bis- (2-bromo-benzenesulfonyl) -, -Ν '^, Ν ¹¹ ' -bis- (2-fluoro-benzenesulfonyl) -, -N ¹¹ JN ' ¹ ' -bis- (2-methyl-benzenesulfonyl ) -, -N ¹ ', N ¹ ''-bis- (2-trifluoromethyl-benzenesulfonyl) -, -N ¹¹ JN ¹¹ ' -bis- (2-methoxy-benzenesulfonyl) -, -N ¹ ', N ^f ''-bis- (2-phenyl-benzenesulfonyl) - and -N ¹ ', N ¹ ' ¹ -bis- (2-methoxycarbonyl-benzenesulfonyl) - -guanidine.

The sulfonyl guanidine derivatives to be used as starting materials of formula (II) are the subject of a previous, but not part of the prior art prior art Patent application by the applicant (see DE-OS 3 334 455).

The compounds of the formula (II) are obtained by using guanidine derivatives of formula (IV),

v ^H / 2
HN - NO

^ C ^ (IV)

or ^

in which

2 3
R and R have the meanings given above,

with sulfonic acid chlorides of the formula (V)

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(V)

in which

R has the meaning given above,

in the presence of acid acceptors, such as ζ. B. pyridine or diazabicyclooctane (DABCO), and optionally in the presence of diluents, such as. B. methylene chloride or chloroform, at temperatures between -20 ⁰ C and +50 ⁰ C, preferably at 0 to 30 ⁰ C is implemented. The work-up can be carried out in the usual way, for example by adding water ^ if necessary acidifying z. B. with hydrochloric acid, extraction with a practically water immiscible solvent, such as. B. methylene chloride or chloroform, washing the organic phase with water, drying, filtering and concentrating. The remaining residual gas in the residue of formula (II) can be brought in general with organic solvents for crystallization, and optionally purified by crystallization order.

The guanidine derivatives of the formula (IV) required as intermediates are also the subject of those mentioned above prior patent application by the applicant (see DE-OS 3 334 455).

These guanidine derivatives are obtained if one cyanaminover-

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-JM-

compounds of the formula (VI)

NC-NH-R ² (VI)

in which

2
R has the meaning given above,

with hydroxylamine derivatives of the formula (VII)

H ₂ N-OR ³ (VII)

in vi / elcher

R ^ has the meaning given above, or their hydrochlorides

optionally in the presence of diluents, such as. B. ethanol or butanol, at temperatures between 20 ⁰ C and 150 ⁰ C, preferably between 50 ⁰ C and 120 ⁰ C, and optionally then with acid acceptors, such as. B. (aqueous) ammonia, sodium hydroxide or potassium carbonate treated. The guanidine derivatives (IV) are generally obtained in crystalline form.

The cyanamino compounds of formula (VI) are in part

known (see J. Chem. Soc. 1953 , 1725-1730).

These compounds are essentially obtained by the following two synthetic routes:

(1) generally by reacting alkali metal or alkaline earth metal salts of cyanamide - such as B. sodium cyanamide or calcium cyanamide - with halogen compounds

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- 21st

of formula (VIII)

Hal ^] -R ² (VIII)

in which

R has the meaning given above and

Shark for fluorine, chlorine, bromine or iodine, in particular

stands for chlorine,

optionally in the presence of inert diluents, such as. B. acetone, acetonitrile or dimethylformamide, at temperatures between 0 ⁰ C and 150 ⁰ C, preferably between 10 ° ^{C and 100 0} C; after the volatile component has been distilled off and the residue has been dissolved in water, the cyanamino compounds of the formula (VI) can be acidified, e.g. B. with hydrochloric acid, precipitated and isolated by suction; or

(2) in the event that R represents a substituted pyrimidinyl radical, by reacting cyanoguanidine ('dicyandiamide') with β-dicarbonyl compounds, such as. B. acetylacetone (cf. J. Chem. Soc. 1953 , 1725 1730), acetoacetic acid esters (cf. J. Prakt. Chem. 77 , (1908), 542 and J. Chem. Soc. 1948, 586) or malonic acid esters (cf. DE-PS 158 591). The 2-cyanamino-4-hydroxy-6-methyl - or -4, 6-di-hydroxy-pyrimidines obtained from acetoacetic acid esters or malonic acid esters can be prepared in a known manner by reaction with alkylating agents, such as. B. dimethyl or diethyl sulfate, optionally in the presence of diluents, such as. B. water, methanol, ethanol, n- and iso-propanol, acetone, dioxane or dimethylformamide, and in the presence of acid binders, such as. B. Le A 23 309

Sodium or potassium hydroxide, sodium or potassium carbonate, be converted into corresponding 2-cyanamino-4-alkoxy-6-methyl- or -4,6-dialkoxypyrimidines. To avoid N-alkylation, if necessary with an acylating agent, such as. B. acetic anhydride or acetyl chloride and acylated after the alkylation is deacylated again with aqueous acids or bases.

The halogen compounds of the formula (VIII) are known (see J. Chem. Soc. (C) 1966 , 2031; Chem. Pharm. Bull. 1 ± (1963), 1382-1388; Arch. Pharm. ^ 9_5 (1962) , 649 657).

The hydroxylamine derivatives of the formula (VII) are known or can be prepared by processes known per se (cf. Chem. Pharm. Bull. 21 (1967), 345-349; Bull. Soc. Chim. France 1958 664; Synthesis 1976 , 682).

Some of the sulfonic acid chlorides of the formula (V) are known (cf. Chemistry Lett. 1978 , 951; EP-PA 23 422, 35 893, 42 731, 44 808, 44 809, 51 466, 64 804 and 70 041; US Pat. PS 2,929,820, 4,282,242 and 4,372,778; J. Org. Chem. 22 (1968), 2104).

These compounds are essentially obtained by the following two synthetic routes:

(1) by converting the corresponding sulfonic acids R SO3H or of their alkali metal or alkaline earth metal salts with halogenating agents, such as. B. phosphorus (V) chloride (Phosphorus pentachloride), phosphoryl chloride (phosphorus oxychloride), thionyl chloride, phosgene or Benzotrichloride, optionally in the presence of catalysts, such as. B. pyridine or dimethylformamide,

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and optionally using inert diluents, such as. B. methylene chloride, chloroform, acetonitrile, chlorobenzene and / or sulfolane at temperatures between -20 ⁰ C and +150 ⁰ C, preferably between 0 ⁰ C and +100 ⁰ C; After dilution with water, the sulfonic acid chlorides - if they are obtained in crystalline form - can be isolated by suction or by extraction with a water-immiscible solvent, such as. B. methylene chloride, diethyl ether or hexane, washing and drying the extracts, concentration and recrystallization or distillation can be purified; or

(2) in a manner known per se (cf. J. Org. Chem. 25 (1960), 1824; DE-OS 2 308 262 and EP-PA 59 241) by reacting corresponding amino compounds R -NH2 with sodium nitrite and hydrochloric acid, if necessary in the presence of acetic acid, at temperatures between -10 ⁰ C and +20 ⁰ C, preferably between -5 ⁰ C and +10 ⁰ C, and then (in situ) with sulfur dioxide or a salt of sulfurous acid, such as. B. sodium sulfite or sodium hydrogen sulfite in the presence of a copper compound, such as. B. copper chloride or copper sulfate, as a catalyst at temperatures between 0 ⁰ C and 80 ⁰ C, preferably between 10 ⁰ C and 60 ⁰ C.

The work-up can be carried out in the usual way:

When diluted with water, the sulfonic acid chlorides fall generally crystalline and can be isolated by suction. But you can also from the watery Dispersion with a practically water immiscible solvent, such as. B. methylene chloride or Diethyl ether, extracted, dried and purified by vacuum distillation.

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- ti -

Those in the process according to the invention continue to be used as starting materials Compounds to be used are generally defined by the formula (III). In this formula has preferably

Az has the same meaning as above in the context of the definition of substituents of formula (I) is preferably mentioned and

M preferably represents hydrogen, lithium, sodium or potassium.

Starting materials of the formula (III) are particularly preferred, in which Az has the same meaning as described above in the context of the definition of substituents of the formula (I) as in particular is mentioned as preferred and M represents hydrogen.

Examples of the starting materials of the formula (III) are called:

Pyrazole, 3,5-dimethylpyrazole, 4-chloropyrazole, 4-bromopyrazole, 4-iodo-pyrazole, 4-chloro-3,5-dimethyl-pyrazole, Imidazole, 2-methyl-imidazole, 2-ethyl-imidazole, 2-propylimidazole, 2-isopropyl-imidazole, 4-methyl-imidazole, 4-ethylimidazole, 4-nitro-imidazole, 2-methyl-4-nitro-imidazole, 2-methyl-5-nitro-imidazole, 4-methyl-5-nitro-imidazole, 2,4-dimethyl-imidazole and 1,2,4-triazole.

The azoles of the formula to be used as starting materials (III) are known.

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The inventive method is preferably carried out in the presence carried out by diluents. Practically all inert organic solvents are preferred as such however, aprotic polar solvents can be used. These include halogenated hydrocarbons, such as. B. Methylene chloride, chloroform, 1,2-dichloroethane and chlorobenzene, Ketones such as B. acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone, esters such as z. B. methyl acetate and ethyl acetate, nitriles, such as. B. acetonitrile and propionitrile, ether, such as B. diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, Tetrahydrofuran and dioxane, amides, such as. B. dimethylformamide and dimethylacetamide, as well as dimethyl sulfoxide and sulfolane.

The inventive method is preferably carried out in the presence carried out by bases. The usual acid acceptors come into consideration, but are preferably nucleophilic Nitrogen compounds which have practically no or only very low proton donor properties. For this include trialkylamines such as B. trimethylamine, triethylamine, Tripropylamine and tributylamine, dialkyl-aralkylamine, such as B. N, N-dimethyl-benzylamine and N, N-diethylbenzylamine, Dialkyl-arylamines, such as. B. N, N-dimethylaniline and N, N-diethyl-aniline, and nitrogen heterocycles, such as. B. Pyridine, 2-methyl-pyridine, 2-methyl-5-ethyl-pyridine, 4-dimethyl-aminopyridine and diazabicyclooctane (DABCO).

In the process according to the invention, the reaction temperatures can be varied within a relatively wide range. In general, one works between 0 ⁰ C and 100 ⁰ C,

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preferably between 10 ^° C. and 80 ^° C.

The inventive method is in general at Normal pressure carried out.

To carry out the method according to the invention sets one per mole of sulfonylguanidine derivative of the formula (II) im generally between 1 and 5 mol, preferably between 1 and 3 mol of a compound of the formula (III) and optionally between 0.01 and 5 moles, preferably between 0.1 and 3 moles, of a base.

The reaction components are usually combined at room temperature and the reaction mixture is stirred until the end of the reaction. If the products are obtained in crystalline form, they can be isolated by suction will. Otherwise it is concentrated and crystallized with a suitable solvent.

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The active ingredients according to the invention can be used as defoliants, Desiccants, haulm killers and especially as weed killers can be used. Under weeds in the broadest sense all plants are to be understood which grow in places where they are undesirable. If she Substances according to the invention act as total or selective herbicides, depends essentially on the applied Amount from.

The active ingredients of the present invention can be used, for example, in the following Plants are used:

Dicot weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus / Ipomoea, Polygonum, Sesbania, Ambrosia, Cir-15. sium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea.

Dicot cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita.

Monocot weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleusocharis, Scumir , Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera.

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3A31926

- ■ M "-

Monocot cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Seeale, Sorghum, Panicum, Saccharum, Ananas, Asparagus, Allium.

However, the use of the active ingredients according to the invention is in no way restricted to these genera, but extends in the same way to other plants.

The compounds are suitable depending on the concentration for total weed control, e.g. on industrial and rail systems and on paths and squares with and without Tree cover. Likewise, the compounds for weed control in permanent crops, e.g. forest, ornamental wood, Fruit, wine, citrus, nut, banana, coffee, tea, rubber, oil palm, cocoa, berry fruit and hop plants and used for selective weed control in annual crops.

The active compounds according to the invention can be used for selective control monocotyledon and dicotyledon weeds in monocotyledon and dicotyledon crops, especially in dicotyledon crops such as cotton, are used, pie active ingredients according to the invention also show a fungicidal effect against Pyricularia oryzae on rice. I.

Le A 23 309

, it-

The active ingredients can be converted into the usual formulations, such as solutions, emulsions, wettable powders, Suspensions, powders, dusts, pastes, soluble powders, granulates, suspension-emulsion concentrates, Active substance-impregnated natural and synthetic substances as well as fine encapsulation in polymeric substances.

These formulations are prepared in a known manner, e.g. by mixing the active ingredients with extenders, that is, liquid solvents and / or solid carriers, optionally using surface-active substances Agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents.

₁ Jm case of the use of water as an extender, organic solvents can also as Hilfslö * example - are used solvents. The following liquid solvents are essentially: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylene or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. petroleum fractions, mineral and vegetable oils, Alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.

The following can be used as solid carriers:

z. B. ammonium salts and natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite,

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- 2tf --hi-

Montmorillonite or diatomaceous earth and synthetic stones, such as highly dispersed silica, aluminum oxide and silicates, come as solid carriers for granulates in question: e.g. broken and fractionated natural rocks such as calcite, marble / pumice, sepiolite, dolomite and synthetic granules made from inorganic and organic flours and granules made from organic material such as sawdust, Coconut shells, corn on the cob and tobacco stalks; as emulsifying and / or foam-producing agents are possible: e.g. non-ionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, Polyoxyethylene fatty alcohol ethers, e.g. alkylaryl polyglycol ethers, alkyl sulfonates, Alkyl sulfates, aryl sulfonates and protein hydrolysates; Possible dispersants are: e.g. lignin sulphite waste liquors and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-like polymers can be used, such as Gum arabic, polyvinyl alcohol, polyvinyl acetate, as well natural phospholipids such as cephalins and lecithins and synthetic phospholipids. Other additives can be mineral and vegetable oils.

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- 29 -

"St.

There can be dyes such as inorganic pigments such as iron oxide, titanium oxide, ferrocyan blue and organic Dyes such as alizarin, azo and metal phthalocyanine dyes; and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95% by weight of active ingredient, preferably between 0.5 and 90%.

The active ingredients according to the invention can be used as such or are also used in their formulations as a mixture with known herbicides for combating weeds, with Ready-made formulations or tank mixes are possible.

Known herbicides such as e.g.

N- (2-Benzthiazolyl) -N, N'-dimethylurea, 3- (3-chloro-4-methylphenyl) -1,1-dimethylurea, 3- (4-isopropylphenyl) -1,1-dimethylurea, 4-Amino-6- (1,1-dimethylethyl) -3-methylthio-1,2,4-triazin-5 (4H) -one, 4-Amino ~ 6- (1, 1- <dimethyl-ethyl) -3-ethylthio-1,2,4-triazin-5 (4H) -one, 1-Amino-6-ethylthio-3- (2,2-dimethylpropyl) -1,3,5-triazine-2,4- (1H, 3H) -dione, 4-amino-3-methyl-6-phenyl-1,2,4-triazin-5 (4H) -one, 2-chloro-4-ethylamino-6-isopropyl-amino-1,3,5-triazine, the R-enantiomer of 2- / 4- (3,5-dichloropyridin-2-oxy) -phenoxy7 ~ propionic acid- (Trimethylsilyl) methyl ester, the R enantiomer of 2- ^ 4- (3,5-dichloropyridyl-2-oxy) -phenoxy ^ Z-propionic acid- (2-benzyloxy) -ethyl ester, 2,4-dichlorophenoxyacetic

Le A 23 3.09

acid, 2- (2,4-dichlorophenoxy) propionic acid, 4-chloro-2-methyl-phenoxy-acetic acid, 2- (2-methyl-4-chlorophenoxy) propionic acid, 3,5-diiodo-4-hydroxy-benzonitrile, 3,5-dibromo-4-hydroxy-benzonitrile as well as diphenyl ethers and phenyl pyridazines such as pyridates. Some mixes Surprisingly, they also show a synergistic effect.

Also a mixture with other known active ingredients, such as fungicides, insecticides, acaricides, nematicides, Protective substances against bird damage, plant nutrients and Soil structure improvers is possible.

The active ingredients can be prepared as such, in the form of their formulations or those prepared therefrom by further dilution Application forms such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granulates can be applied. They are used in the usual way, e.g. by watering, spraying, atomizing, scattering.

The active compounds according to the invention can be applied both before and after emergence of the plants will.

they can also be incorporated into the soil before sowing.

The amount of active ingredient used can be greater Area fluctuate. It essentially depends on the type of effect desired. Generally lying the application rates between 0.001 and 10 kg of active ingredient per hectare of soil, preferably between 0.05 and 5 kg per ha.

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-3T-

The manufacture and use of the inventive Active ingredients can be seen from the following examples.

Le A 23 309

Preparation examples Example 1

/ \ VsOo-NΛΪ * 'Ν

H, C

A mixture of 5.9 g (0.01 mol) N '- (4,6-dimethyl-pyrimidin-2-yl) -N "- methoxy-N", N "" - (2-methoxy- carbonyl-benzenesulfonyl) guanidine, 1.1 g (0.011 mol) of 3,5-dimethyl-pyrazole, 3.0 g (0.03 mol) of triethylamine and 30 ml of acetone is stirred for 2 days at 2O ⁰ C. The crystalline product is isolated by suction.

You get. 2.7 g (61% of theory) of the compound of the structural formula given above with a melting point of 164 ^° C.

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Similarly, those listed in Table 1 below can be used Compounds of the formula (I) are established:

Table 1

Az

E.g.
No.

Melting point (° C)

Cl

, Cl

CH ₃ CH ₃

CH ₃

H ₃ C

I.

197

214

198

178

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At game 6

, NW ^CH3

H / ι ^ A

Ν ^ Ν-ί 'Μ χ H ₂ SO ₄

I ^{N =} ^ CH,

A mixture of 2.9 g (0.66 mol) of the product from BeispieH, 0.8 g (0.08 mol) of sulfuric acid and 20 ml of acetone is stirred for 4 hours at 2O ⁰ C. The crystalline product is then isolated by suction.

1.8 g (51% of theory) of the product of the formula given above with a melting point of 182 ^° C. are obtained.

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-55 "- Production of starting materials of the formula (II)

Example (II-1)

A mixture of 29.4 g (0.15 mol) of N '- (4,6-dimethyl-pyrimidin-2-yI) -N''- methoxy-guanidine, 63.6 g (0.3 mol) of 2- Chlorobenzenesulfonic acid chloride and 150 ml of pyridine are ^{stirred at 20 °} C. for 2 days. After the pyridine has been largely removed by distillation in a water-streaked vacuum, the residue is mixed with 200 ml of water and extracted with 200 ml of methylene chloride. The organic phase is separated off, dried and concentrated. The residue is reduced by digestion with ethanol Brought crystallization.

41.2 g (51% of theory) N '- (4,6-Dimet hy I-pyrimidin-2-yl) -N ^II -methoxy-N' ^I -N ^III -bis- (2-chloro- ben2olsulfonyl) guanidine with a melting point of 164 ° C to 166 ° C.

The compounds of the formula (II) listed in Table 2 below can be prepared analogously:

I.
R ¹ -SO ₂ ^/

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Tabel

Example No. Melting point ( ⁰ C)

II-2 II-3 II-4 II-5 II-6 II-7 II-8 II-9 11-10

, COOCH3

, ^CH 3

/ W

CF ₃

Br

OCH3

OCF ₃

OCHF?

J »X

XN = /

f ^

CH ₃

H ₃ CH ₃

CH ₃ CH ₃

CH ₃ CH ₃

CH ₃ CH ₃

n = /

CH ₃

CH ₃ CH ₃

CH ₃ CH ₃

CH ₃ CH ₃

CH ₃

CH ₃

CH ₃

CH ₃

CH ₃

CH ₃

CH ₃

CH ₃

CH ₃

165

129

171

121

147

166

196

158

163

Le A 23

Table 2 - continued

Example No. Melting point ^)

11-11 II -12 11-13 11-14 11-15 11-16

SO ₂ N (CH ₃ )?

COOCpH ₅

COOC ₄ H ₉

C00C3H7

SO ₂ CH ₃

CH ₃

CH ₃ CH ₃ CH ₃ CH ₃ CH ₃ CH ₃

155

138

106

104

134

Le A 23

Preparation of starting materials in the formula (IV) Example (IV-D

OCH ₃

A mixture of 109 g (0.67 mol) of O-methyl I hydroxy I amine hydrochloride 99 g (0.67 moles) of 2-cyanamino-4,6-dimethy I-pyrimidine and 600 ml of ethanol is refluxed for 7 hours. Then the alcohol distilled off in a water jet vacuum, the residue in dissolved in hot water and added this solution to 100 ml of concentrated ammonia. The crystallized product is filtered off with suction and recrystallized from ethanol.

71.8 g (55 % of theory) of N '- (4,6-Dimet hylpyrimidin-2-yI) -N "-methoxy-guanidiη with a melting point of 134 ° C to 136 ° C are obtained.

Le A 23 309

Production of starting materials of the formula (V) Example (VD

295 ml phosphoryl chloride ( 'phosphorus') are grown at 20 ⁰ C to 3O ⁰ C was added dropwise to a mixture of 172 g (0.8 mol) of 2-chloro-benzenesulfonic acid-NatriumsaIz, 300 ml of acetonitrile and added 300 ml of sulfolane. The reaction mixture is stirred for 4 hours at 70 ⁰ C, then cooled to 5 ° C and diluted with ice water. After extracting with petroleum ether, washing the extraction solution with water, drying, filtering and concentrating, the product remaining in the residue is purified by vacuum distillation.

This gives 117 g (70 X of theory) of 2-chloro ~ benzoIsuIfonsäurechlorid of boiling point 110 ° C / 1.1 mbar.

Example (V-2)

Le A 23 309

75.5 g (0.5 mol) of methyl 2-aminobenzoate are dissolved in 176 ml of concentrated hydrochloric acid and 100 ml of acetic acid. For this purpose, a solution of 34.4 g of sodium nitrite in 70 ml of water is added dropwise ^{at 0 ° C.} After stirring for a further 15 minutes, the reaction mixture is slowly added to a saturated solution of sulfur dioxide in 450 ml of acetic acid that has been cooled to ^{0 ° C.} After removal of the cooling bath, the mixture is stirred until the evolution of gas has ended, 10 g of copper (II) chloride being added in portions. After diluting with ice water, extracting with methylene chloride, washing the extraction solution with water, drying, filtering and concentrating, the product remaining in the residue is purified by vacuum distillation.

45 g (38% of theory) of 2-methoxycarbonyI-benzene sulfonic acid chloride with a boiling point of 150 ° C./1.33 bar are obtained.

Analogously, the table 3 below can be used th compounds of the formula (V) are prepared:

R ¹ - SO ₂ -Cl (V)

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Tabel

Example no.

Boiling point / pressure

V-3

V-4

V -S V-6

V -7

V -8

V -9

V -10 V-Il

V -12

V -13

V -14

CH,

O ₂ N (CH ₃ )

₃ ) ₂

NS

, SCH (CH ₃ ) ₂

U-

XCH ₂ SO ₂ CH ₃

COOC ₂ H ₅

(OeI, decomposition during distillation)

[Melting point: 100 ⁰ C] (OEI)

142 ⁰ C / 4 inbar 106 ° C / 4 mbar [melting point: 32 ⁰ C]

(OeI, decomposition during distillation)

[Melting point: 103 ⁰ C]

(OeI, decomposition during distillation)

90 ° C / 1, 33 Rabar [melting point: 12O ⁰ C]

2 ir.bar

Le A 23

-JrZ-

Example a

Pre-emergence test

Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether

For the production of an appropriate preparation of the active substance if 1 part by weight of active ingredient is mixed with the stated amount of solvent, the stated amount of emulsifier is added and dilute the concentrate with water to the desired concentration.

Seeds of the test plants are sown in normal soil and, after 24 hours, watered with the preparation of the active compound. The amount of water per unit area is expediently kept constant. The active ingredient concentration in the preparation does not play a role, only the application rate of the active ingredient per unit area is decisive. After three weeks, the degree of damage to the plants is rated in% damage in comparison to development the untreated control. It means:

0% = no effect (like untreated control) 100% = total destruction

In this test, for example, the following compounds of the preparation examples show excellent effectiveness: (1), (2), (4) and (5)

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Example B.

Post-emergence test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active ingredient, 1 part by weight of active ingredient is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with it
Water to the desired concentration.

Test plants 5-15 cm in height are sprayed with the preparation of active compound in such a way that the particular amounts of active compound desired are applied per unit area. The concentration of the spray liquor is chosen so that the particular amounts of active compound desired are applied in 2000 1 of water / ha. After three weeks, the degree of damage to the plants
rated in% damage in comparison to the development of the untreated control.
It means:

O% = no effect (like untreated control) 100% = total destruction

In this test, for example, the following compounds show the production Examples of excellent effectiveness: (D, (2), (4) and (5).

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Claims (5)

Claims 1) Amidinoazoles of the general formula (I) Az in which R is an optionally substituted radical from Series alkyl, aralkyl, aryl and heteroaryl, R represents an optionally substituted and / or optionally fused six-membered aromatic heterocycle containing at least one nitrogen atom contains, stands and Az is an optionally substituted azole radical, d. ft. a five-membered aromatic heterocycle, u / elchp contains at least one nitrogen atom, as well as adducts as compounds of the formula (I) with strong acids. 2) Process for the preparation of amidinoazoles of the general formula (I) according to claim 1, characterized in that sulfonylguanidine derivatives of the formula (H) Le A 23 309 R ¹ -50 ₂ -N ^V - ^H ^ 'NR ² R-SO ₂ ^ in which 1 2
R and R have the meanings given above and R for an optionally substituted carbon hydrogen residue is with compounds of the formula (III) M-Az (III) in which Az has the meaning given above and M represents hydrogen or a metal equivalent, optionally in the presence of bases and in the presence of diluents at temperatures between 0 ^° C. and 100 ^° C. and optionally treating the products of the formula (I) obtained in this way with acids. 3) Herbicidal agents, characterized by a content of at least one amidinoazole of the general formula (I) according to claim 1. Le A 23 309 4) Use of amidinoazoles of the general formula (I) according to claim 1 for combating undesired plant growth . 5) Process for the preparation of herbicidal agents, thereby characterized in that one amidinoazole of the general Formula (I) according to Claim 1 mixed with extenders and / or surface-active agents. Le A 23 309